Azo anthraquinone vat dyestuffs



United States Patent cc 2,705,709

Patented Apr. 5, 1955 substitution product being formed either simultaneously 2,705,709 with diaiotization by the actiofn lot (the hydrofluoric acid or y su sequent conversion 0 t e iazo compound into AZO ANTHRAQUINONE VAT DYESTUFFS the fluorine substitution product with the splitting off of 5 nitrogen. In the resulting 1-fluoro-2-methyl-4- or -5-chlo- Eduard gfif j hgzf i figf g g fi gf to Ciba robenzene the methyl group is either oxidized directly to a carboxylic acid group or converted into a trichloro- No Drawing. Original application December 17, 1951, methyl group followed by hydrolysis of the latter to a Serial No. 262,173. Divided and this application May carboxyllc and p- 23, 1954 serial 433,306 The l amino-5-(2'-fluorobenzoylamino) anthraquinone or 1-amino-5-(2'-fiuoro-4' or -5-chlorobenzoylami- Claims priority, application Switzerland June 3, 1949 no)-anthraquinone is acylated with acylating agents derived for example from 1:1-azobenzcne-3:3- or -4:4'-di 6 Claims- (CL 260-2074) earboxylic acid or azodiphenyl dicarboxylic acids. In all cases it is of advantage to carry out the acylation This apphcatloh 1s a dlvlsloh of my copendmg P with the aid of reactive derivatives of the carboxylic acids cation h 5 on December 12511 in question. The reaction may be conducted in a solvent which itself is a continuation in part of my applleation or dispersing medium advantageously 0f high befling sfirial 100,293: filed June 1949 how abahdonedpoint such as mono-, dior tri-chlorobenzene, nitrobenzene Thiipfesellt invention is based on the Observation that 20 or naphthalene at a raised temperature, for example,

valuable dyfismfis are PF h one molech' within the range from about 100 C. to the boiling point P P Q of all y t agent del'lved P an of the solvent or dispersing medium used. azobenze fi lq rb ylw ffhm an alodlphenyl The products of the invention are valuable vat dyedjcarboxyllc 5 15 reacted with two molecular P 'P stuffs. They can be used in known manner as such or tlo ls 0f 'P Y h in form of their leuco-ester salts obtainable by known none, l fluorohehlpylamlno) methods for dyeing and printing a very wide variety of '?q 'fiuofohenzoyl fibers of animal and especially vegetable character, thus am1n0)an thraquln0l1ewool and silk, but especially Eotton, linen, and artificial Accofdlngly the new dyestuffs correspond to the silk or staple fibers or regenerated cellulose and also mula 3 superpolyamide fibers.

RC0--NH o o HN-OC-R The following examples illustrate the invention the parts and percentages being by weight unless otherwise stated and the relationship of parts by Weight to parts by volume being the same as that of the kilogram to the liter:

' Example 1 g o-NH 0 A mixture of 4.22 parts of azodiphen yl-dicarboxylic wherein X stands for a member selected from the group acid of the formula consisting of an azobenzene radical and an azo diphenyl 16 parts of thionyl chloride, 0.05 part of pyridine and radical and R stands for a member selected from the gro p 290 parts of trichlorobenzene is heated in about 2 hours consisting of the radicals corresponding to the formulae fro 0 c, to boiling temperature, Th parts of the solvent are distilled off and 7.5 parts of l-amino 5 C1 5 (2'-fluorobenzoylamino)-anthraquinone are added at about 100 C. and the whole is heated again to boiling and kept at this temperature for 2 hours while stirring. The difiicultly soluble dyestuff of the formula QCO-NH o A HNOCQ and is filtered off at 120 C. and washed with alcohol. It is 01 soluble in concentrated sulfuric acid with an orange coloration and dyes cotton from a bordeaux colored hydrosulfite vat in very fast full yellow shades.

When instead of azodiphenyl-diicarboxylic acid an equivalent quantity of 1:1-azobenzene-4:4'-dicarboxylic acid fisl usedi a dyestuiff is obtainled wlcilicllli also cllgi es cota ton ulyelowtints romaruyre yrosu tevat. g fig g i gfi g i -$3 95 fggggggffgg, 2 5 1;; With lzl'-azobenzene-3:3'-dicarboxylic acid there is obdiaminoanthraquinone The or 5 1 tamed a dyestuif WhlCh dyes cotton from a ruby red hybenzoic acid which are neeess for introducin the cordrosulfite Vat h Yellow i The responding acyl radicals can be h iade by methods in themq a nt aq mone employed can be obselves known A suitable method for preparing such tamed by partial acylation of l:5-d1am1no-an.thraqumone compounds consists, for example, in diazotizing l-aminowith the ortho-fluorobenzoyl chloride or from l-chloro- 2-mcthyl-4- or -chlorobenzene with the aid of hydro- 5-(ortho-fluorobenzoylamino)-anthraquinone by replacefluoric acid and sodium nitrite, the appropriate fluorine ment of the chlorine atom by the toluene sulphonamide residue and splitting off of the sulphonic acid residue. It crystallizes from pyridine or nitrobenzene in fine red crystals which melt at 269.5270 C. (uncorrected).

Example 2 G I-QC O BN 1 (i N11 to The 2-fiuoro-4-chlorobenzoic acid can advantageously be prepared by the oxidation with potassium permanganate of 2-fiuoro-4-chlorotoluene (boiling at 158 C. under 743 mm. pressure), which latter can be obtained from 2- amino-4-chloro-toluene by the hydrofiuoboric acid method of Balz and Schiemann (Berichte der deutschen Chemischen Gesellschaft, vol. 60, page 1188 (1927)) in excellent yield. In an analogous manner 2-fluoro-5-chlorobenzoyl chloride (boiling at 103-104 C. under 15 mm. pressure) can be obtained from 2-amino-5-chloro-toluene by way of the intermediate products 2-fiuoro-5-chlorotoluene (boiling at 156 C. under 741 mm. pressure) and 2-fluoro-5-chlorobenzoic acid (melting at 149150 C.).

I NH!) to What is claimed is:

1. An anthraquinone vat RC 0-NH O dyestufi of the formula 0 HNOC--R H o HN--OC-XC O-NH 0 wherein X stands for a member selected from the group I II III IV Color of the Anthraqumongoltomponent, 2 Acid component 1 mol Dyc girtignon hydrosttlmm 1 1 amino-5- (2- throw-4- chloroa-z0benzeue-3:3-dicarboxylic inll yellow. b o r d e a u x benzoylamino) anthraquiacid. red. none. 2 1 amino-5-(2-fluo1'o-5 ch10r0- 10 do bordeaux.

benzoylarnino) anthraquinone. 3 d0 azodigl lcnyl dicarboxylic golden yellow. Do.

aci

The l-amino-S-(4-chloro-2'-1luorobenzoylamino)- anthraquinone used (melting point 279 C.) can be made by the partial acylation of 1:5-diaminoanthraquinone with 2- fluoro-4-chlorobenzoyl chloride, or from 1-chloro-5-(4- chloro-2'-fluorobenzoylamino)-anthraquinone by replacing the chlorine atom by a toluene sulfonamide radical fol lowed by splitting off of the sulfonic acid radical. l-amino- 5-(5-chloro 2 fluorobenzoylamino) anthraquinone (melting point 269 C.) can be made in the same manner.

2fluoro-4-chlorobenzoyl chloride (boiling at IDS-106 C. under 14mm. pressure) can be made from 2-fluoro-4- chlorobenzoic acid (melting point 205 C.) by reaction with thionyl chloride.

Q0 O-NH consisting of an azobenzene radical and an azo diphenyl rad1c al and R stands for a member selected from the group consisting of the radicals corresponding to the formulae and 6 3. The anthraquinone vat dyestufi of the formula OL-Q-CO-NH o HN-OC-QC] 3 HN 0 0 n 3 N 4. The anthraquinone vat dyestufl? of the formula 01 Cl C0-NH O 5. The anthraquinone vat dyestuff of the formula QGO-NH o o HN-OCQ 6. The anthraquinone vat dyestufi of the formula HW N= No references cited. 

1. AN ANTHRAQUINONE VAT DYESTUFF OF THE FORMULA 